Mixed guanidin derivatives and process of making same.



UNITED STATES PATENT? OFFICE.

AD OLF ISRAEL AND RICHARD KOTHE, OF ELBERFELD, GERMANY, ASSIGNORS TOFARBENFABRIKEN OF ELBERFELD 00., OF NEW YORK, N. Y.

MIXED GUANIDIN DERIVATIVES AND PROCESS OF MAKING SAME.

SPECIFICATION formingpart of Letters Patent No. 677,515, dated July 2,1901.

Application filed February 20, 1901. Serial No. 48,168. (Specimens) Toall whom, it may concern:

Be it known that we, ADOLF ISRAEL and RICHARD KOTHE,doctors ofphilosophy, chemists, (assignors to the FARBENFABRIKEN or ELBERFELDCOMPANY, of New York,) residing at Elberfeld, Germany, have invented anew and useful Improvement in Mixed Guanidin Derivatives and Processesof Making Same and we hereby declare the following to be a clear andexact description of our invention.

Our invention relates to the production of new mixed guanidinderivatives having the following general formula:

(R meaning in this formula a hydrogen atom which can be substituted by afatty or an aromatic radicalsuch as methyl, phenyl, oxynaphthyl,oxynaphthyl sulfonic acid, or the like.)

The process for producing the said guanidin derivatives consists intreating mixed thio-urea compounds with ammonia or with primary fatty oraromatic amins-such as methylamin, anilin, paraphenylenediamin,amidonaphthol, amidonaphthol sulfonic acid, or the likein the presenceof agents capable of absorbing sulfureted hydrogen, such as lead oxid orthe like. The said mixed thiourea compounds can be prepared,forinstance, by treating with carbon bisulfid, sulfur, and alcohol anequimolecular mixture of two different amidonaphthol sulfonic acidswhich do not contain the amido and the hydroxy group either in theso-called ortho position or in the so-called peri position. The newguanidin derivatives thus obtained are in the shape of the sodium saltsgrayish powders readily soluble in hot and soluble in cold water andbeing soluble with difficulty in dilute mineral acids. They can becombined with diazo compounds, valuable azo dyestuffs being thus produced.

In carrying out our new process practically we can proceed as follows,the parts being by weight: 56.5 parts of the sodium salt of thiocarbonyldioxydinaphthylamin disulfonic acid (obtained from an equimolecularmixture of beta -amido-alpha -naphthol beta sulfonic acid and beta-amido-alpha,-naphtholbeta -sulfonic acid) having the following formula:

are dissolved in about four hundred parts of hot water. After theaddition of from nine to ten parts of a twenty-per-cent. ammoniasolution and from fifty to sixty parts of care fully-pulverized leadoxid the mixture thus obtained is heated in a vessel provided with areflux condenser by means of a water-bath with continuous stirring.After a short time the color of the lead oxid begins to grow black bythe transformation into lead sulfid. The reaction is finished when thequantity of the latter no longer increases. Subsequently the reactionmixture is filtered, mixed with an excess of hydrochloric acid, and theguani din derivative thus produced is precipitated from the filtrate bythe addition of common salt, filtered off, and dried. It is then furtherpurified by dissolving it in a sodiunrcarbonate solution andprecipitating it again by the addition of common salt.

The new guanidin derivative having in a free state the followingformula:

molecules of diazo compounds, thus furnish- 7 ing valuable azodyestuffs.

The process proceeds in an analogous man ner if instead of ammonia otherof the abovementioned amins are used.

Having now described our invention and in what manner the same is to beperformed, what we claim as new, and desire to secure by Letters Patent,is-' 1. The process for producing new guanidin derivatives having thehereinbefore-defined general formula:

which process consists in heating the hereindefined mixed thio-ureacompounds of amidonaphthol sulfonic acids with amins in the presence ofagents capable of absorbing sulfureted hydrogen, and then isolating theguanidiu derivatives thus produced, substantially as 'hereinbeforedescribed.

2. The process for producing a new guanidin derivative having in a freestate the fol lowing formula:

alpha -naphthol-beta -sultonic acid and from beta, amido alpha naph'tholbeta -sulfonic acid with ammonia and lead oxid, and then isolating thenew guanidin derivative thus produced, substantially as hereinbeforedescribed.

3. The'h'e rein-d'ejscribed new mixed guani din derivatives ofamidonaphthol sulfonic acids which, in the shape of the sodium salts,

, are grayish powders readily soluble in hot and soluble in cold water,being soluble with difficulty in dilute mineral acids and being capableof combining with diazo compounds,

valuable az'o dy'stufis being thus produced, substantially ashereinbefore described.

at. The herein'described new mixed guanidin derivative derived from beta-amido-alpha -naphthol-b'eta -sulfonic acid and from beta amid o-alpha'naphtliolbetag s ulfonic' acid which, in the shape-of the sodium'salt,is a grayish powder soluble in cold and readily soluble in hot-water,being" soluble with ditiiculty inalcohol and insoluble inether and beingcapable of c'ombining'with one and'like wisewith two molecules of diazocompounds;

valuable a'zo dyestuffs being thus-produced, substantially ashereinbefore'described;

In testimony whereof We have signed our names in the presence oftwo'subscribing w'i'tnesses.

ADOLF ISRAEL. RICHARD KOTHE. lVitnesses:

OTTO KoNIG,

EMIL BLOMBERG.

